Catalytic dehydrogenation reactions find extensive applications in chemical industries production and hydrogen fuel production. It is therefore critical to develop efficient dehydrogenation catalysts that adapt to harsh reaction conditions. Layered double hydroxides (LDHs) have provided extensive applications in catalytic dehydrogenation because of its special two-dimensional layered structure, flexible adjustable of metal cations, and easy exchange of intercalated anions, which provides many intelligent design strategies for catalytic dehydrogenation applications. This article mainly reviews LDHs and their hybrid materials as catalysts, catalyst precursors or supports, and focus on their research progress in hydrogen storage materials dehydrogenation, direct dehydrogenation and oxidative dehydrogenation reactions. Furthermore, methods of preparing LDHs are briefly introduced. Finally, prospective research on LDHs and its derivatives used as catalytic materials in the field of catalytic dehydrogenation are proposed.